JPH08157786A - Double-coated tape - Google Patents

Abstract

PURPOSE: To prepare a double-coated tape improved in blocking resistance and punching accuracy by providing a specific heat-sensitive adhesive layer on one surface of a base material and a pressure-sensitive adhesive layer on the other surface of the base material. CONSTITUTION: A solid plasticizer in an amount of 100 pts.wt. if necessary, coated with resin particles having a glass transition temp. of 50 deg.C or above and a particle size of at most 10μm is blended with 20-200 pts.wt. thermoplastic resin having a glass transition temp. of -5 to 50 deg.C and 5-100 pts.wt. tackifier having a softening temp. of 80 deg.C or above and, if necessary, a colloid of an inorg. or org. compd. to obtain a heat-sensitive adhesive. One surface of a base material 9 such as paper, nonwoven fabric, woven fabric, film or foam is coated with the heat-sensitive adhesive to form a heat-sensitive adhesive layer 10, while the other surface thereof is coated with a pressure-sensitive adhesive to form a pressure-sensitive adhesive layer 8, on which a separator 7 is provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is non-tacky at room temperature but develops tackiness upon heating, and
The present invention relates to a double-sided tape having a heat-sensitive adhesive layer on one side of which the tackiness is maintained for a while even after removing the heating source, and further having a pressure-sensitive adhesive layer on one side.

[0002]

2. Description of the Related Art A conventional double-sided tape is also called a double-sided adhesive tape or a double-sided adhesive tape. As shown in FIG. 1, a tape body having a pressure-sensitive adhesive layer 2 on both sides of a base material 3 and its adhesiveness are protected. 1 separator 1 (also called a liner or release liner), or FIG.
As shown in FIG. 3, it is composed of a tape main body having pressure sensitive adhesive layers 5 on both sides of a base material 6 and two separators 4 for protecting the adhesiveness thereof. In general, the tape body is often wound in a roll shape together with the separator, and it can be processed into various forms such as a flat sheet shape such as a sheet or film having an appropriate size depending on the application. .

The separator is necessary to protect the surface of the pressure-sensitive adhesive layer, and is a release paper obtained by releasing the surface of papers such as high-quality paper and glassine paper with a silicone resin or the like, or a silicone resin or the like. A plastic film coated with a mold agent or a plastic film alone is usually often used, but usually, in order to perform release treatment on both sides, when punching to produce a desired label, seal or sheet, There has been a problem that the pressure-sensitive adhesive layer and the release paper slip and are displaced. further,
Since the base material has pressure-sensitive adhesive layers on both sides, during punching, the pressure-sensitive adhesive adheres to the blade to be punched, which easily causes blade stains, and the pressure-sensitive adhesive does not stick to the cut surface. It adheres. For example, when making a floppy disk or optical disk, a double-sided tape is punched out and used in a ring shape to fix the metal hub and the disk (magnetic disk or optical disk), but there is a problem in punching precision. It was

In order to solve this problem, attempts have been made to devise a release agent for the separator to produce a non-slip separator. However, due to the relationship between the release agent and the pressure-sensitive adhesive, it is special. However, there is a problem in cost and the like. Further, in order to prevent the blade from being soiled and adhered by the pressure-sensitive adhesive layer, methods such as thinning the pressure-sensitive adhesive layer have been devised, but there is a problem in that there is a limit to the countermeasures in terms of adhesive performance. There was a point. Further, the conventional double-sided tape is often used in the form of FIG. In this case, the separator will be sandwiched between the pressure-sensitive adhesive layers, and when using this double-sided tape (in order to use,
The separator must always be attached to one of the pressure sensitive adhesive layers (for a certain length). Furthermore, when sticking, this separator must peel off.

In order to satisfy the above-mentioned conditions (different peelability), 1) the peelability to the pressure-sensitive adhesive layer is changed between the front and back of the separator (that is, the releasing treatment is changed to the front. Or 2) by changing the type of pressure-sensitive adhesive (including adding different additives) to change the adhesiveness to the separator, or both 1) and 2). It is necessary to do. However, in order to carry out the means of 1) and / or 2), it is necessary to devise a great deal.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a double-sided tape having a heat-sensitive adhesive layer on one side and a pressure-sensitive adhesive layer on one side, which has excellent blocking resistance. Is provided.

[0007]

That is, the present invention provides a thermoplastic resin having a glass transition temperature of -5 ° C or higher on one surface of a substrate,
Provided is a double-sided tape having a heat-sensitive adhesive layer containing a tackifier and a solid plasticizer, and having a pressure-sensitive adhesive layer on one side. As shown in FIG. 3, the double-sided tape of the present invention comprises a separator 7, a pressure-sensitive adhesive layer 8, a substrate 9 and a heat-sensitive adhesive layer 10 having blocking resistance. Usually, the mold release treatment of the separator is performed on one surface in contact with the pressure-sensitive adhesive layer 8. As the base material, paper, non-woven fabric, woven cloth, film, foam or the like which has been used as a base material for conventional double-sided adhesive tape or double-sided adhesive tape can be used. Examples of the paper include Japanese paper, high-quality paper, glassine paper and the like, and examples of the non-woven fabric include non-woven fabric such as rayon, polyester and polypropylene. Examples of the woven cloth include woven cloth of natural fibers or synthetic fibers such as cotton cloth, suf, and vinylon, and examples of the film include films of polyester (especially polyethylene terephthalate), polyvinyl chloride, polypropylene, cellophane and the like. Examples of the foam include polyurethane, polyethylene, butyl rubber, chloroprene, vinyl chloride, and acrylic rubber.

As the pressure-sensitive adhesive, commonly used rubber-based, acrylic-based, vinyl-based, or silicon-based adhesives are used. For example, "Adhesion Handbook" (Second Edition, Showa 55)
Yearly, published by Nikkan Kogyo Shimbun) can be used. The basic skeleton is an elastic resin, a tackifier, a plasticizer and other fillers, and an additive. As the resin of the pressure-sensitive adhesive, for example, natural rubber, synthetic isoprene rubber, recycled rubber, acrylic acid ester, styrene-acrylic acid ester, styrene-butadiene, ethylene-vinyl acetate, vinyl acetate, vinyl acetate-acrylic acid ester, Examples thereof include polymers such as ethylene-vinyl chloride, ethylene-acrylic acid ester, ethylene-acrylic acid, butadiene, urethane, styrene-isoprene, acrylonitrile-butadiene, isobutylene, and vinyl ether.

Examples of tackifiers for pressure-sensitive adhesives include terpene resins, aliphatic petroleum resins, aromatic petroleum resins, coumarone-indene resins, styrene resins, phenol resins, terpene-phenol resins, rosin derivatives ( Examples thereof include rosin, polymerized rosin, hydrogenated rosin, esters thereof with glycerin and pentaerythritol, and resin acid dimer). As the plasticizer for the pressure-sensitive adhesive, a plasticizer that is liquid at room temperature is mainly used, and examples thereof include mineral oil, lanolin, liquid polybutene, and liquid polyacrylate.

Other fillers and additives for the pressure-sensitive adhesive include zinc oxide, calcium carbonate, clay, aluminum hydroxide, pigments, and antioxidants for rubber. The resin, tackifier, plasticizer or other fillers and additives which are elastic bodies of the pressure-sensitive adhesive can be used alone or as a mixture of two or more kinds. The pressure sensitive adhesive can be coated on the substrate as an aqueous emulsion type, a water soluble type, a hot melt type, a solventless type or an organic solvent type. The heat-sensitive adhesive has a solid skeleton, a thermoplastic resin, and a tackifier as a basic skeleton. For example, those described in "Adhesion Handbook" (12th edition, 1980, published by Kobunshi Kogyokai) Can be used. Thermoplastic resins are the source of tackiness and adhesiveness, and solid plasticizers give little plasticity to the resin because they are solid at room temperature, and when heated, they melt and swell or soften the resin. Therefore, the thermosensitive adhesive, which is non-adhesive at room temperature, has the function of exhibiting adhesiveness by heating. At this time, when the tackifier is present, the tackiness becomes more remarkable, and the practical properties are improved.

The glass transition temperature of the thermoplastic resin is -5 ° C in order to improve the blocking resistance of the heat-sensitive adhesive layer.
However, in the case of ethylene-vinyl acetate, 0 ° C or higher is preferable. However, if the glass transition temperature is too high, the film-forming property will be deteriorated.
Less than is preferred. Further, when the thermoplastic resins are mixed and used, the value calculated from the glass transition temperature of each thermoplastic resin assuming that the additivity is established according to the weight ratio, or actually performing thermal analysis of the mixture At least one of the values should fall within the temperature range of the present invention. In order to further improve the blocking resistance of the heat-sensitive adhesive layer, in the composition of the heat-sensitive adhesive, 1) use of a solid plasticizer having a high melting point, 2) surface treatment of the solid plasticizer, 3) softening temperature Use of a high tackifier, 4) addition of the third component, etc. may be performed.

As for "1) Use of solid plasticizer having high melting point", it is preferable to use solid plasticizer having a melting point of 50 ° C or higher, more preferably 60 ° C or higher. When the solid plasticizers are mixed and used, the value calculated as the additivity is established depending on the weight ratio from the melting point of each solid plasticizer,
Alternatively, at least one of the values obtained by actually performing thermal analysis of the mixture may fall within the above range. Regarding "2) Surface treatment of solid plasticizer", it is preferable to coat the surface of the solid plasticizer with an inorganic compound and / or resin fine particles. Even if the solid plasticizer has a melting point or less, it melts to some extent to give plasticity to the resin depending on conditions such as storage temperature, so that there is a problem in blocking resistance. However, it is considered that by coating the surface of the solid plasticizer with the inorganic compound and / or the resin fine particles, the melting of the solid plasticizer is suppressed and the blocking resistance is improved.

Examples of the inorganic compound include oxides, hydrates, inorganic acid salts, organic acid salts, ammonium salts, metal compounds, and special compounds such as colloids. It may be appropriately selected depending on the compatibility with the thermoplastic resin, tackifier or solid plasticizer used in the heat-sensitive adhesive, cost, and the like. More specifically, oxides, hydroxides, oxyhydroxides, nitrates, carbonates, phosphates, sulfates, oxalates, acetates, tartrates and citrates are used. Specific examples of the inorganic compound include oxides such as magnesium oxide, aluminum oxide, titanium oxide, barium oxide, titanium barium oxide, aluminum barium oxide, magnesium aluminum oxide, and aluminum silicon oxide, magnesium hydroxide, aluminum hydroxide, and water. Barium oxide, talc, calcium carbonate,
Examples include barium sulfate.

As the colloid, colloids of inorganic compounds and organic compounds can be used.
Examples thereof include molecular colloids such as proteins or elastic rubbers, micellar colloids formed from soaps, particle colloids such as oxide sols and metal sols, and particle colloids are particularly preferable. There are various types of particle colloids depending on the combination of the dispersoid and the dispersion state of the dispersion medium, and examples of the oxide sol include colloidal silica, alumina sol, antimony oxide sol, and zirconia sol. Examples of the metal sol include gold sol and selenium sol. Further, smectite and the like, which are fine clay minerals and become a sol when dispersed in water or the like, can be mentioned.

The resin fine particles are preferably those having a glass transition temperature of 50 ° C. or more and an average particle diameter of 10 μm or less, and are used as a thermoplastic resin, a tackifier or a solid plasticizer used in a heat-sensitive adhesive. It may be appropriately selected depending on the compatibility or cost. As a use form, it can be used in the form of powder or emulsion. When resin fine particles are used, those having a substantially spherical shape are preferable.
Examples of the resin fine particles include, but are not limited to, styrene polymer powder, ethylene polymer powder, methyl methacrylate polymer powder, and methyl methacrylate-styrene copolymer powder.

The resin fine particles may be dispersed in a solvent and added, or may be added as it is. A known solvent can be appropriately used as the dispersion solvent, and the dispersion solvent is not limited to the organic solvent, and may be an inorganic solvent or, of course, water. As a method of coating the surface of the solid plasticizer with an inorganic compound and / or resin fine particles,
(1) A method of softening or melting the surface of the solid plasticizer by heat, (2) a method of using a binder, (3) a method of mechanical impact means, and the like, but not limited to these. Absent. The above method and apparatus are specifically described in "Granulation Handbook" (1st edition, 1991, published by Ohmsha).

As the method (1), a fluidized coating device, a tumbling coating device or a pan coating device is used to heat the entire device by the heat of a heating medium (water or the like), thereby allowing the surface of the solid plasticizer to be heated. A method of coating the inorganic compound and / or resin fine particles by softening or melting the resin, or by directly softening or melting the surface of the plasticizer with hot air or the like. Examples of the method (2) include a method of coating a solid plasticizer with an inorganic compound by supplying a binder into the apparatus using a fluidized coating apparatus, a tumbling coating apparatus or a pan coating apparatus. Any binder can be used as long as it can bond the solid plasticizer with the inorganic compound and / or the resin fine particles, and for example, polyvinyl alcohol, gelatin, gum arabic, dextrin, natural rubber, sodium alginate and the like can be used.

Examples of the method (3) include an impact method in a high-speed air stream, in which an inorganic compound and / or
Alternatively, resin fine particles can be coated. When coating the surface of the solid plasticizer with an aqueous dispersion such as a colloid, (1) after mixing and dispersing the solid plasticizer in the aqueous dispersion such as a colloid, heating and / or depressurizing the dispersion medium completely or Partial evaporation, (2) evaporation of a dispersion medium in which an aqueous dispersion such as a colloid is dispersed, and then coating in the same manner as in the case of the inorganic compound and / or resin fine particles, However, the present invention is not limited to these.

"3) Use of tackifier having high softening temperature"
With respect to, it is preferable to use a tackifier having a softening temperature of 80 ° C. or higher, more preferably 100 ° C. or higher. Regarding “4) addition of third component”, an inorganic compound (preferably colloid) and / or resin fine particles are added to the heat-sensitive adhesive.
It is appropriately selected and contained depending on the compatibility with the thermoplastic resin used in the heat-sensitive adhesive, the tackifier and the solid plasticizer, the cost or the like. As the inorganic compound and / or resin fine particles, those described in the above “2) Surface treatment of solid plasticizer” can be used, but particles having a particle size of 10 μm or less are particularly preferable. Hard particles having a glass transition temperature of 50 ° C. or higher are preferred.

Examples of the solid plasticizer of the heat-sensitive adhesive include diphenyl phthalate, dihexyl phthalate, dicyclohexyl phthalate, dihydroabietyl phthalate, dimethyl isophthalate, sucrose benzoate, ethylene glycol dibenzoate, tribenzoic acid. Trimethylolethane,
Tribenzoic acid glyceride, tetrabenzoic acid pentaerythritol, sucrose octaacetate, tricyclohexyl citrate,
Examples thereof include N-cyclohexyl-p-toluenesulfonamide, and dicyclohexyl phthalate is preferable. Further, the thermoplastic resin of the heat-sensitive adhesive is preferably used in a solid content ratio of 20 to 200 parts by weight, and further 30 to 140 parts by weight with respect to 100 parts by weight of the solid plasticizer. Examples of the thermoplastic resin include acrylic acid ester, styrene-acrylic acid ester, styrene-butadiene, ethylene-vinyl acetate, vinyl acetate, vinyl acetate-acrylic acid ester,
Ethylene-vinyl chloride, ethylene-acrylic acid ester, ethylene-acrylic acid, butadiene, urethane, styrene-isoprene, isoprene, acrylonitrile-
Examples thereof include polymers such as butadiene, isobutylene, and vinyl ether.

The tackifier for improving the adhesive performance of the heat-sensitive adhesive is 5-10 parts by weight per 100 parts by weight of the solid plasticizer.
It is preferably used in a solid content ratio of 0 part by weight, more preferably 10 to 50 parts by weight. Examples of the tackifier include terpene resin, aliphatic petroleum resin, aromatic petroleum resin, coumarone-
Examples thereof include indene resin, styrene resin, phenol resin, terpene-phenol resin, and rosin derivative (rosin, polymerized rosin, hydrogenated rosin and their glycerin, esters with pentaerythritol, resin acid dimer, etc.). The solid plasticizer, thermoplastic resin or tackifier of the heat-sensitive adhesive may be used alone or in a mixture of two or more.

That is, the solid plasticizer of the heat-sensitive adhesive is
Dicyclohexyl phthalate and diphenyl phthalate,
Dicyclohexyl phthalate and dihexyl phthalate,
Dicyclohexyl phthalate and dihydroabietyl phthalate, Dicyclohexyl phthalate and dimethyl isophthalate, Dicyclohexyl phthalate and sucrose benzoate, Dicyclohexyl phthalate and Ethylene glycol dibenzoate, Dicyclohexyl phthalate and Trimethylolethane tribenzoate, Dicyclohexyl phthalate And tribenzoic acid glyceride, dicyclohexyl phthalate and pentaerythritol tetrabenzoate, dicyclohexyl phthalate and sucrose octaacetate, dicyclohexyl phthalate and tricyclohexyl citrate,
Dicyclohexyl phthalate and N-cyclohexyl-p-
It is also possible to use two kinds with toluenesulfonamide or the like or a mixture of three kinds or more with dicyclohexyl phthalate, diphenyl phthalate and dihexyl phthalate and the like.

The tackifier for the heat-sensitive adhesive is a terpene resin and an aliphatic petroleum resin, an aromatic petroleum resin and a coumarone-indene resin, a styrene resin and a phenol resin, a terpene-phenol resin and a rosin derivative. Two types of terpene resin and rosin derivative, aliphatic petroleum resin and rosin derivative, aromatic petroleum resin and rosin derivative, coumarone-indene resin and rosin derivative, styrene resin and rosin derivative, phenol resin and rosin derivative 3 with rosin derivatives, aliphatic petroleum resins and aromatic petroleum resins
It can also be used in a mixture of types or more.

Further, the thermoplastic resin of the heat-sensitive adhesive includes acrylic acid ester and styrene-acrylic acid ester, styrene-butadiene and ethylene-vinyl acetate, vinyl acetate and vinyl acetate-acrylic acid ester, ethylene-vinyl chloride and ethylene. -Acrylic acid esters, ethylene-acrylic acid and butadiene, urethane and styrene-isoprene, styrene-butadiene and acrylic acid esters, styrene-butadiene and styrene-acrylic acid esters, styrene-butadiene and vinyl acetate, styrene-butadiene and vinyl acetate- Acrylic ester, styrene-butadiene and ethylene-vinyl chloride, styrene-butadiene and ethylene-acrylic ester, styrene-butadiene and ethylene- Acrylic acid, styrene - butadiene and butadiene, styrene - butadiene and urethane, styrene - butadiene and styrene - isoprene, styrene - butadiene and acrylonitrile -
It is also possible to use two kinds of butadiene or the like or a mixture of three kinds or more of styrene-acrylic acid ester, styrene-butadiene, ethylene-vinyl acetate and the like.

The heat-sensitive adhesive can be coated on the substrate as an aqueous emulsion or an organic solvent solution,
Considering the handling of the tape after coating and drying, it is preferable to coat it as an aqueous emulsion. Other fillers and the like may be added to the pressure-sensitive adhesive and the heat-sensitive adhesive. As the filler and the like, for example,
Inorganic substances such as zinc oxide, calcium carbonate, clay, aluminum hydroxide, titanium oxide, alumina, kaolin, talc, colloidal silica and alumina sol, paraffin,
Examples thereof include organic substances such as natural wax, synthetic wax, natural oil and fat, and resin powder. Further, a solvent, a liquid plasticizer, etc. may be added for the purpose of improving the film-forming property of the coating film. Further, if necessary, a dispersant, a defoaming agent, a thickener, etc. can be used.

In general, the double-sided tape of the present invention is prepared by applying a heat-sensitive adhesive and a pressure-sensitive adhesive on one surface of a substrate and then (when it is applied as an aqueous emulsion or water-soluble adhesive). After drying, or when coated as an organic solvent solution (only the heat-sensitive adhesive), after release of the tackiness by drying), a separator (usually one side in contact with the pressure-sensitive adhesive layer is subjected to a release treatment). However, it can be processed into various forms such as a flat sheet or a sheet or a film having an appropriate size depending on the intended use.

[0027]

EXAMPLES The present invention will be specifically described below with reference to examples. However, the scope of the present invention is not limited to the following examples. In the examples, “part” means “part by weight”,
% Represents% by weight. [Examples 1 to 4] (Pressure-sensitive adhesive) A base material and a curing agent of the pressure-sensitive adhesive manufactured by Toyo Ink Mfg. Co., Ltd. shown in Table 1 were mixed and stirred in a mixer to prepare a coating sample.

(Heat-sensitive adhesive) Fluid coating device (Fuji Paudal Co., Ltd. Numalmelizer NQ-L)
ABO), dicyclohexyl phthalate (melting point 65 ℃) 300
And 30 parts of titanium oxide were charged, and the surface of dicyclohexyl phthalate was coated with titanium oxide by hot air. As a result of observing the coating state of titanium oxide-coated dicyclohexyl phthalate with a scanning electron microscope, it was confirmed that dicyclohexyl phthalate was coated with titanium oxide.

Next, the formulation shown in Table 1 was mixed and stirred in a mixer for 5 minutes to prepare a heat-sensitive adhesive. [Examples 5 to 6] (Pressure-sensitive adhesive) A base material and a curing agent of the pressure-sensitive adhesive manufactured by Toyo Ink Mfg. Co., Ltd. shown in Table 1 were mixed and stirred in a mixer to prepare a coated sample. (Heat-sensitive adhesive) Using the same apparatus as in Example 1, 300 parts of magnesium oxide was coated on the surface of 300 parts of diphenyl phthalate (melting point: 69 ° C) with hot air. It was confirmed as in Example 1 that diphenyl phthalate was coated with magnesium oxide.

Then, a heat-sensitive adhesive was prepared in the same manner as in Example 1 according to the formulation shown in Table 1. [Example 7] (Pressure Sensitive Adhesive) In the same manner as in Example 1, the main component and curing agent of the pressure sensitive adhesive manufactured by Toyo Ink Mfg. Co., Ltd. shown in Table 1 were used.
Mixing and stirring were performed in a mixer to prepare a coated sample. (Heat-sensitive adhesive) The same apparatus as in Example 1 was charged with 300 parts of dicyclohexyl phthalate and 30 parts of titanium oxide, and a solution of 3% acrylic polymer in n-butyl alcohol was used as a binder. Coated with titanium oxide. It was confirmed as in Example 1 that dicyclohexyl phthalate was coated with titanium oxide.

Then, a heat-sensitive adhesive was prepared in the same manner as in Example 1 according to the formulation shown in Table 1. Example 8 (Pressure Sensitive Adhesive) As in Example 1, the main component and curing agent of the pressure sensitive adhesive manufactured by Toyo Ink Mfg. Co., Ltd. shown in Table 1 were used.
Mixing and stirring were performed in a mixer to prepare a coated sample. (Heat-sensitive adhesive) 300 parts of diphenyl phthalate and 30 parts of aluminum oxide were charged into a tumbling coating device (High-speed mixer LFS-1 manufactured by Fukae Kogyo Co., Ltd.), and the surface of diphenyl phthalate was coated with aluminum oxide by heating. . It was confirmed as in Example 1 that the diphenyl phthalate was coated with aluminum oxide.

Then, a heat-sensitive adhesive was prepared in the same manner as in Example 1 according to the formulation shown in Table 1. [Example 9] (Pressure Sensitive Adhesive) As in Example 1, the main component and curing agent of the pressure sensitive adhesive manufactured by Toyo Ink Mfg. Co., Ltd. shown in Table 1 were used.
Mixing and stirring were performed in a mixer to prepare a coated sample. (Heat-sensitive adhesive) 300 parts of dicyclohexyl phthalate and 30 parts of titanium oxide were charged into a powder surface reforming device (hybridization system NHS-O manufactured by Nara Machinery Co., Ltd.) using the high-speed air impact method. The surface of dicyclohexyl phthalate was coated with titanium oxide by mechanical impact. As in Example 1, it was confirmed that dicyclohexyl phthalate was coated with titanium oxide.

Then, a heat-sensitive adhesive was prepared in the same manner as in Example 1 according to the formulation shown in Table 1. Example 10 (Pressure Sensitive Adhesive) As in Example 1, the main ingredient and curing agent of the pressure sensitive adhesive manufactured by Toyo Ink Mfg. Co., Ltd. shown in Table 2 were used.
Mixing and stirring were performed in a mixer to prepare a coated sample. (Heat-sensitive adhesive) 150 parts of colloidal silica (solid content 20%) and 300 parts of dicyclohexyl phthalate were mixed and dried in a mixer, and then placed in a glass beaker according to the formulation shown in Table 2,
Mixing was performed with a mixer to prepare a heat-sensitive adhesive. It was confirmed as in Example 1 that dicyclohexyl phthalate was coated with colloidal silica.

Example 11 (Pressure Sensitive Adhesive) As in Example 1, the main components and curing agent of the pressure sensitive adhesive manufactured by Toyo Ink Mfg. Co., Ltd. shown in Table 2 were used.
Mixing and stirring were performed in a mixer to prepare a coated sample. (Heat-sensitive adhesive) 150 parts of alumina sol (solid content 20%) and 300 parts of diphenyl phthalate were mixed and dried in a mixer, then placed in a glass beaker having the composition shown in Table 2 and mixed by a mixer. A heat sensitive adhesive was prepared. Diphenyl phthalate is coated with alumina sol,
Confirmed in the same manner as in Example 1.

Example 12 (Pressure Sensitive Adhesive) As in Example 1, the main components and curing agent of the pressure sensitive adhesive manufactured by Toyo Ink Mfg. Co., Ltd. shown in Table 2 were used.
Mixing and stirring were performed in a mixer to prepare a coated sample. (Heat-sensitive adhesive) Using the same apparatus as in Example 1, 150 parts of zirconia sol (solid content 20%) and dicyclohexyl phthalate 3
00 parts were charged and the surface of dicyclohexyl phthalate was coated with zirconia sol with hot air. The coating of dicyclohexyl phthalate with zirconia sol was confirmed as in Example 1.

Then, a heat-sensitive adhesive was prepared in the same manner as in Example 1 according to the formulation shown in Table 2. Example 13 (Pressure Sensitive Adhesive) As in Example 1, the main agent and curing agent of the pressure sensitive adhesive manufactured by Toyo Ink Mfg. Co., Ltd. shown in Table 2 were used.
Mixing and stirring were performed in a mixer to prepare a coated sample. (Heat-sensitive adhesive) Using the same apparatus as in Example 8, 150 parts of colloidal silica (solid content 20%) and dicyclohexyl phthalate were used.
300 parts were charged and colloidal silica was coated on the surface of dicyclohexyl phthalate using a 3% acrylic polymer solution in n-butyl alcohol as a binder. It was confirmed in the same manner as in Example 1 that dicyclohexyl was coated with colloidal silica and phthalic acid.

Then, a heat-sensitive adhesive was prepared in the same manner as in Example 1 according to the formulation shown in Table 2. Example 14 (Pressure Sensitive Adhesive) As in Example 1, the main ingredient and curing agent of the pressure sensitive adhesive manufactured by Toyo Ink Mfg. Co., Ltd. shown in Table 2 were used.
Mixing and stirring were performed in a mixer to prepare a coated sample. (Heat-sensitive adhesive) Example 13 except that half of the colloidal silica (75 parts) was replaced with alumina sol (solid content 20%).
A heat-sensitive adhesive was prepared in the same manner as in. It was confirmed as in Example 1 that dicyclohexyl phthalate was coated with colloidal silica and alumina sol.

Then, a heat-sensitive adhesive was prepared in the same manner as in Example 1 according to the formulation shown in Table 2. Example 15 (Pressure Sensitive Adhesive) As in Example 1, the main agent and curing agent of the pressure sensitive adhesive manufactured by Toyo Ink Mfg. Co., Ltd. shown in Table 2 were used.
Mixing and stirring were performed in a mixer to prepare a coated sample. (Heat-sensitive adhesive) 30 parts of powder obtained by drying colloidal silica in a dryer was coated on the surface of 300 parts of dicyclohexyl phthalate by heating using the same apparatus as in Example 8. As in Example 1, it was confirmed that dicyclohexyl phthalate was coated with colloidal silica.

Then, a heat-sensitive adhesive was prepared in the same manner as in Example 1 according to the formulation shown in Table 2. Example 16 (Pressure Sensitive Adhesive) As in Example 1, the main agent and curing agent of the pressure sensitive adhesive manufactured by Toyo Ink Mfg. Co., Ltd. shown in Table 2 were used.
Mixing and stirring were performed in a mixer to prepare a coated sample. (Heat-sensitive adhesive) Using the same device as in Example 1, 300 parts of dicyclohexyl phthalate and methyl methacrylate-styrene copolymer powder (particle size 0.2 to 0.5 μm, Tg = 128 ° C., spherical powder manufactured by Soken Chemical Co., Ltd.) ) 30 parts, and the surface of dicyclohexyl phthalate was coated with methyl methacrylate-styrene copolymer powder by hot air. It was confirmed in the same manner as in Example 1 that dicyclohexyl phthalate was coated with the methyl methacrylate-styrene copolymer powder.

Then, a heat-sensitive adhesive was prepared in the same manner as in Example 1 according to the formulation shown in Table 2. Example 17 (Pressure Sensitive Adhesive) As in Example 1, the main ingredient and curing agent of the pressure sensitive adhesive manufactured by Toyo Ink Mfg. Co., Ltd. shown in Table 2 were used.
Mixing and stirring were performed in a mixer to prepare a coated sample. (Heat-sensitive adhesive) Using the same apparatus as in Example 8, 150 parts of diphenyl phthalate, 150 parts of dicyclohexyl phthalate and methyl methacrylate-styrene copolymer powder (particle size)
0.4 μm, Tg = 95 ° C, spherical powder made by Soken Chemical Industry Co., Ltd.) 30
Then, the surfaces of diphenyl phthalate and dicyclohexyl phthalate were coated with a methyl methacrylate-styrene copolymer powder with hot air. It was confirmed in the same manner as in Example 1 that diphenyl phthalate and dicyclohexyl phthalate were coated with the methyl methacrylate-styrene copolymer powder.

Then, a heat-sensitive adhesive was prepared in the same manner as in Example 1 according to the formulation shown in Table 2. Example 18 (Pressure Sensitive Adhesive) As in Example 1, the main component and curing agent of the pressure sensitive adhesive manufactured by Toyo Ink Mfg. Co., Ltd. shown in Table 2 were used.
Mixing and stirring were performed in a mixer to prepare a coated sample. (Heat-sensitive adhesive) Using the same device as in Example 9, 300 parts of diphenyl phthalate and methyl methacrylate-styrene copolymer powder (particle size 0.2 to 0.5 μm, Tg = 128 ° C., spherical powder manufactured by Soken Chemical Co., Ltd.) ) 30 parts were charged and the surface of diphenyl phthalate was coated with a methyl methacrylate-styrene copolymer powder by mechanical impact. It was confirmed in the same manner as in Example 1 that the diphenyl phthalate was coated with the methyl methacrylate-styrene copolymer powder.

Then, a heat-sensitive adhesive was prepared in the same manner as in Example 1 according to the formulation shown in Table 2. [Examples 19 to 26] (Pressure-sensitive adhesive) As in Example 1, the main component and curing agent of the pressure-sensitive adhesive manufactured by Toyo Ink Mfg. Co., Ltd. shown in Table 3 were used.
Mixing and stirring were performed in a mixer to prepare a coated sample. (Heat-sensitive adhesive) The composition shown in Table 3 was mixed with a mixer to prepare a heat-sensitive adhesive.

In Example 19, half of colloidal silica (75 parts) was added and mixed, and then half of colloidal silica (75 parts) was added and mixed. In Example 24, half the amount (15 parts) of methyl methacrylate-styrene copolymer powder (particle size 0.2 to 0.5 μm, Tg = 128 ° C., spherical powder manufactured by Soken Kagaku Co., Ltd.) was added and mixed. Further, a half amount (15 parts) of the methyl methacrylate-styrene copolymer powder was added and mixed. [Comparative Examples 1 to 3] Commercially available double-sided tapes shown in Table 4 were used.

In Examples 1 to 26, the obtained pressure-sensitive adhesive was coated on one surface of a high-quality paper so that the coating amount was 40 g / m ² , dried at 100 ° C. for 2 minutes, and then coated. Place the separator on the work surface, and then apply the heat-sensitive adhesive on one side and
It was coated at 30 g / m ² and dried at 40 ° C for 5 minutes to obtain a double-sided tape. No adhesiveness was confirmed in the heat-sensitive adhesive layer after drying. As the separator, a separator subjected to release treatment only on the side in contact with the pressure-sensitive adhesive layer was used. The obtained double-sided tape was left for 7 days in a room at 25 ° C. and 60% (aged), and then evaluated for adhesive strength, holding power, cutting resistance and blocking resistance, and the results are shown in Tables 1 to 4.
Shown in The evaluation was performed by the following method.

Adhesion: The double-sided tapes of Examples 1 to 26 were measured by the following two methods. 1) Without heating, after cutting to a predetermined length, the separator is peeled off and the pressure-sensitive adhesive layer side is attached to a stainless steel plate. 2) After heating at 120 ° C for 30 seconds to develop the adhesiveness of the heat-sensitive adhesive layer, the heat-sensitive adhesive layer side is quickly attached to the stainless steel plate with the separator attached.

Further, the roll-shaped double-sided tapes of Comparative Examples 1 to 3 are cut to a predetermined length with the separator attached and attached to a stainless steel plate. According to JIS K-6848, the pasted product was peeled by 180 degrees to measure the adhesive strength, and judged according to the following criteria. However, the gluing part is 100m
m. ◎ ・ ・ ・ ・ ・ ・ 800g / 25mm or more ○ ・ ・ ・ ・ ・ ・ 600g / 25mm or more, less than 800g / 25mm × ・ ・ ・ ・ ・ ・ Less than 600g / 25mm Holding power; Double-sided tape of Examples 1-26 Was measured by the following two methods.

1) Without heating, after cutting to a predetermined length, the separator is peeled off and the pressure-sensitive adhesive layer side is attached to a stainless steel plate. 2) After heating to 120 ° C for 30 seconds to develop the adhesiveness of the heat-sensitive adhesive layer, the heat-sensitive adhesive layer side is quickly attached to the stainless steel plate with the separator attached. Further, the roll-shaped double-sided tapes of Comparative Examples 1 to 3 are cut into a predetermined length while the separator is attached, and attached to a stainless steel plate.

According to JIS K-6848, the attached one is
A creep test was conducted by applying a constant load of 500 g, and the judgment was made according to the following criteria. However, the gluing part was 25 mm. ◎ ・ ・ ・ 2000 seconds or more ○ ・ ・ ・ ・ ・ ・ 1000 seconds or more and less than 2000 seconds × ・ ・ ・ ・ ・ ・ less than 1000 seconds Cleavability: The double-sided tapes of Examples 1 to 26 should be heated. Without the double sided tapes of Comparative Examples 1 to 3,
100 pieces of sample cut to a width of 10 cm and a length of 10 cm are stacked,
The end was cut off using a guillotine cutter, the pressure-sensitive adhesive or the heat-sensitive adhesive on the cut surface of the sample was squeezed out, and the state of adhesion of the adhesive or the like to the blade of the cutter was observed and judged according to the following criteria.

(Protrusion of Pressure-sensitive Adhesive or Heat-sensitive Adhesive to Cut Surface of Sample) ⊚ ··· No protrusion. The stacked samples are separated. ○ ・ ・ ・ ・ ・ ・ There is almost no protrusion. The stacked samples are separated. △: ・ Extrusion is observed, but the stacked samples are scattered. ×: ・ Overhanging is considerably observed, and the overlapped samples do not come apart.

[0050] (guillotine feeling stuck wearing state of the pressure sensitive such as an adhesive or a heat-sensitive adhesive to the blade of the cutter) ◎ ······ sticking there is no or almost none. ○: ・ The blade of the cutter becomes cloudy or some sticking is observed, but when the blade is touched with the hand, almost no tackiness is observed (there is almost no tackiness). X: Adhesion is recognized, and tackiness is recognized when the blade is touched by hand (tackiness is felt).

Blocking resistance: The double-sided tapes of Examples 1 to 26 were prepared by stacking 10 samples which were cut to a width of 10 cm and a length of 10 cm without heating. A load of 500 g / cm ² was applied to these, and they were peeled off after being stored at 50 ° C. for 1 hour, and the blocking resistance of the heat-sensitive adhesive layer was judged according to the following criteria. Further, the double-sided tapes of Comparative Examples 1 to 3 did not undergo the test, because blocking was prevented by the separator. 5: No peeling resistance.

4 ・ ・ Some noise is generated when peeling. 3 ・ ・ A continuous sound is heard when peeling. 2 ・ ・ Pull fiber of paper at the time of peeling. 1 ... · There is breakage of the substrate due to blocking. 0 ... ・ Completely adhere. (Peeling impossible) From the results of Tables 1 to 4, the glass transition temperature of -5 was found on one side of the substrate.
A double-sided tape having a heat-sensitive adhesive layer containing a thermoplastic resin, a solid plasticizer, and a tackifier at a temperature of ℃ or more, and having a pressure-sensitive adhesive layer on one side, the heat-sensitive adhesive layer is resistant to blocking. Excellent in cutting performance, compared to conventional double-sided tape, there are few unnecessary materials such as separators, and because the pressure-sensitive adhesive is applied only on one side, cutting performance is also good, that is, punching accuracy is also good. Is shown.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

[Table 3]

[0056]

[Table 4]

(Notes to Table 1, Table 2, Table 3 and Table 4) * 1 Coated with inorganic compound or resin fine particles * 2 Solid content ratio in solution to total amount * 3 Softening temperature 150 ° C, Arakawa Chemical Co., Ltd. Company * 4 Styrene-butadiene copolymer * 5 Ethylene-vinyl acetate copolymer * 6 Particle size 0.2-0.5 μm, Tg = 128 ° C, Soken Chemical Co., Ltd * 7 Particle size 0.4 μm, Tg = 95 ° C, Soken Chemical Co., Ltd. * 8 Particle size 15-40 μm, Tg = 105 ℃, Soken Chemical Co., Ltd. * 9 Tg = 100 ℃ or more, Pyrolysis temperature 300 ℃, NV = 44%, Mitsui Toatsu Chemical Co., Ltd. * 10 Tg = 100 ° C or higher, thermal decomposition temperature 295 ° C, NV = 35%, Mitsui Toatsu Chemical Co., Ltd. * 11 Tg = 2 ° C, NV = 46%, Johnson Polymer Co., Ltd. * 12 Tg = 6 ° C, NV = 49%, manufactured by Nippon Zeon Co., Ltd. * 13 A: Toyo Ink Mfg. Co., Ltd., pressure-sensitive adhesive main agent, trade name Olivine PS1109 C: Toyo Ink Manufacturing Co., Ltd. pressure sensitive adhesive main agent, trade name Olivine BPS4089 E: Toyo Ink Manufacturing Co., Ltd. pressure sensitive adhesive main agent, trade name Olivine BPS8404 * 14 B: Toyo Ink Manufacturing Co., Ltd. pressure sensitive adhesive Agent curing agent, trade name Olivine BHS8515 D: Toyo Ink Mfg. Co., Ltd. pressure-sensitive adhesive curing agent, trade name Olivine BPS4089B F: Toyo Ink Mfg. Co., Ltd. pressure sensitive adhesive curing agent, trade name Olivine BHS8404B * 15 Pressure-sensitive adhesive Mixing ratio (parts by weight) of the curing agent to 100 parts by weight of the main agent in the adhesive.

* 16 After cutting to a predetermined length without heating, the separator is peeled off, and the pressure-sensitive adhesive layer side is attached to a stainless steel plate. * 17 After heating to 120 ° C for 30 seconds to develop the adhesiveness of the heat-sensitive adhesive layer, the heat-sensitive adhesive layer side is quickly attached to the stainless steel plate with the separator attached. In addition, the roll-shaped double-sided tape of the comparative example is cut into a predetermined length with the separator attached, and attached to a stainless steel plate. * 18 After cutting to a predetermined length without heating, the separator is peeled off and the pressure-sensitive adhesive layer side is attached to a stainless steel plate.

* 19 After heating to 120 ° C. for 30 seconds to develop the tackiness of the heat-sensitive adhesive layer, the heat-sensitive adhesive layer side is quickly attached to the stainless steel plate with the separator attached. In addition, the roll-shaped double-sided tape of the comparative example is cut into a predetermined length with the separator attached, and attached to a stainless steel plate. * 20 Toyo Ink Co., Ltd. double-sided tape, product name DF
-1100 * 21 Double-sided tape manufactured by Nichiban Co., Ltd., product name NW-
40 * 22 Double-sided tape manufactured by Sekisui Chemical Co., Ltd., product name W
3-40C

[0060]

EFFECTS OF THE INVENTION According to the present invention, one side of a substrate has a heat-sensitive adhesive layer containing a thermoplastic resin having a glass transition temperature of -5 ° C or higher, a solid plasticizer and a tackifier, and one side thereof has one side. , The double-sided tape having the pressure-sensitive adhesive layer has excellent blocking resistance in the heat-sensitive adhesive layer, less unnecessary materials such as separators are used as compared with the conventional double-sided tape, and the pressure-sensitive adhesive is coated on only one side. Since it is not formed, the cutting property is good, that is, the punching precision is also good. This makes it possible to provide a resource-saving and economical product as a double-sided tape with few separators, and as a sheet or film.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a conventional double-sided tape having one separator.

FIG. 2 is a cross-sectional view of a conventional double-sided tape having two separators.

FIG. 3 is a cross-sectional view of a double-sided tape used in the present invention.

[Explanation of symbols]

1 Separator 2 Pressure-sensitive adhesive layer 3
Substrate 4 Separator 5 Pressure-sensitive adhesive layer 6
Substrate 7 Separator 8 Pressure-sensitive adhesive layer 9
Substrate 10 Thermosensitive adhesive layer with blocking resistance

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hiroyuki Iida 2-3-13 Kyobashi, Chuo-ku, Tokyo Toyo Inki Manufacturing Co., Ltd. (72) Inventor Makoto Kameyama 2-3-13 Kyobashi, Chuo-ku, Tokyo Toyo Inki Manufacturing Co., Ltd.

Claims (10)

[Claims] 1. A heat-sensitive adhesive layer containing a thermoplastic resin having a glass transition temperature of −5 ° C. or higher, a tackifier and a solid plasticizer on one side of a substrate, and a pressure-sensitive adhesive on one side. A double-sided tape having a layer. 2. The double-sided tape according to claim 1, wherein the glass transition temperature of the thermoplastic resin is less than 50 ° C. 3. A glass transition temperature of 0 as a thermoplastic resin.
The double-sided tape according to claim 1 or 2, wherein an ethylene-vinyl acetate copolymer having a temperature of ℃ or more is used. 4. The double-sided tape according to claim 1, wherein a styrene-butadiene copolymer is used as the thermoplastic resin. 5. The double-sided tape according to claim 1, wherein an acrylic polymer is used as the thermoplastic resin. 6. The double-sided tape according to claim 1, wherein the surface of the solid plasticizer is coated with an inorganic compound. 7. The double-sided tape according to claim 6, wherein the inorganic compound is a colloid. 8. The surface of the solid plasticizer has a glass transition temperature of 50.
The double-sided tape according to any one of claims 1 to 6, which is coated with resin fine particles having a temperature of not less than 0 ° C and an average particle diameter of not more than 10 µm. 9. The double-sided tape according to claim 1, wherein the heat-sensitive adhesive layer further contains a colloid. 10. The double-sided tape according to claim 1, wherein the heat-sensitive adhesive layer further contains resin fine particles having a glass transition temperature of 50 ° C. or more and an average particle diameter of 10 μm or less.